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Article: Cis-dihydroxylation of alkenes with oxone catalyzed by iron complexes of a macrocyclic tetraaza ligand and reaction mechanism by ESI-MS spectrometry and DFT calculations
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TitleCis-dihydroxylation of alkenes with oxone catalyzed by iron complexes of a macrocyclic tetraaza ligand and reaction mechanism by ESI-MS spectrometry and DFT calculations
 
AuthorsChow, TWS1
Wong, ELM1
Guo, Z1
Liu, Y1
Huang, JS1
Che, CM1
 
Issue Date2010
 
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.html
 
CitationJournal Of The American Chemical Society, 2010, v. 132 n. 38, p. 13229-13239 [How to Cite?]
DOI: http://dx.doi.org/10.1021/ja100967g
 
Abstract[FeIII(L-N4Me2)Cl2]+ (1, L-N4Me2 = N,N′-dimethyl-2,11-diaza[3.3](2,6) pyridinophane) is an active catalyst for cis-dihydroxylation of various types of alkenes with oxone at room temperature using limiting amounts of alkene substrates. In the presence of 0.7 or 3.5 mol % of 1, reactions of electron-rich alkenes, including cyclooctene, styrenes, and linear alkenes, with oxone (2 equiv) for 5 min resulted in up to >99% substrate conversion and afforded cis-diol products in up to 67% yield, with cis-diol/epoxide molar ratio of up to 16.8:1. For electron-deficient alkenes including α,β-unsaturated esters and α,β-unsaturated ketones, their reactions with oxone (2 equiv) catalyzed by 1 (3.5 mol %) for 5 min afforded cis-diols in up to 99% yield with up to >99% substrate conversion. A large-scale cis-dihydroxylation of methyl cinnamate (9.7 g) with oxone (1 equiv) afforded the cis-diol product (8.4 g) in 84% yield with 85% substrate conversion. After catalysis, the L-N4Me2 ligand released due to demetalation can be reused to react with newly added Fe(ClO4)2•4H2O to generate an iron catalyst in situ, which could be used to restart the catalytic alkene cis-dihydroxylation. Mechanistic studies by ESI-MS, isotope labeling studies, and DFT calculations on the 1-catalyzed cis-dihydroxylation of dimethyl fumarate with oxone reveal possible involvement of cis-HO-Fe V O and/or cis-O FeV O species in the reaction; the cis-dihydroxylation reactions involving cis-HO-FeV O and cis-O FeV O species both proceed by a concerted but highly asynchronous mechanism, with that involving cis-HO-FeV O being more favorable due to a smaller activation barrier. © 2010 American Chemical Society.
 
ISSN0002-7863
2013 Impact Factor: 11.444
 
DOIhttp://dx.doi.org/10.1021/ja100967g
 
ISI Accession Number IDWOS:000282304000048
Funding AgencyGrant Number
The University of Hong Kong
University Grants Council of HKSARAoE 10/01P
Hong Kong Research Grants CouncilHKU 1/CRF/08
HKU 7007/08P
Funding Information:

This work was supported by The University of Hong Kong (University Development Fund), the University Grants Council of HKSAR (the Area of Excellence Scheme: AoE 10/01P), and the Hong Kong Research Grants Council (HKU 1/CRF/08, HKU 7007/08P). We are grateful to Dr. Nianyong Zhu for assistance in solving the X-ray crystal structures of 1 center dot FeCl<INF>4</INF> and 1 center dot ClO<INF>4</INF>center dot MeCN.

 
ReferencesReferences in Scopus
 
DC FieldValue
dc.contributor.authorChow, TWS
 
dc.contributor.authorWong, ELM
 
dc.contributor.authorGuo, Z
 
dc.contributor.authorLiu, Y
 
dc.contributor.authorHuang, JS
 
dc.contributor.authorChe, CM
 
dc.date.accessioned2011-06-17T09:18:54Z
 
dc.date.available2011-06-17T09:18:54Z
 
dc.date.issued2010
 
dc.description.abstract[FeIII(L-N4Me2)Cl2]+ (1, L-N4Me2 = N,N′-dimethyl-2,11-diaza[3.3](2,6) pyridinophane) is an active catalyst for cis-dihydroxylation of various types of alkenes with oxone at room temperature using limiting amounts of alkene substrates. In the presence of 0.7 or 3.5 mol % of 1, reactions of electron-rich alkenes, including cyclooctene, styrenes, and linear alkenes, with oxone (2 equiv) for 5 min resulted in up to >99% substrate conversion and afforded cis-diol products in up to 67% yield, with cis-diol/epoxide molar ratio of up to 16.8:1. For electron-deficient alkenes including α,β-unsaturated esters and α,β-unsaturated ketones, their reactions with oxone (2 equiv) catalyzed by 1 (3.5 mol %) for 5 min afforded cis-diols in up to 99% yield with up to >99% substrate conversion. A large-scale cis-dihydroxylation of methyl cinnamate (9.7 g) with oxone (1 equiv) afforded the cis-diol product (8.4 g) in 84% yield with 85% substrate conversion. After catalysis, the L-N4Me2 ligand released due to demetalation can be reused to react with newly added Fe(ClO4)2•4H2O to generate an iron catalyst in situ, which could be used to restart the catalytic alkene cis-dihydroxylation. Mechanistic studies by ESI-MS, isotope labeling studies, and DFT calculations on the 1-catalyzed cis-dihydroxylation of dimethyl fumarate with oxone reveal possible involvement of cis-HO-Fe V O and/or cis-O FeV O species in the reaction; the cis-dihydroxylation reactions involving cis-HO-FeV O and cis-O FeV O species both proceed by a concerted but highly asynchronous mechanism, with that involving cis-HO-FeV O being more favorable due to a smaller activation barrier. © 2010 American Chemical Society.
 
dc.description.natureLink_to_subscribed_fulltext
 
dc.identifier.citationJournal Of The American Chemical Society, 2010, v. 132 n. 38, p. 13229-13239 [How to Cite?]
DOI: http://dx.doi.org/10.1021/ja100967g
 
dc.identifier.doihttp://dx.doi.org/10.1021/ja100967g
 
dc.identifier.eissn1520-5126
 
dc.identifier.epage13239
 
dc.identifier.hkuros185855
 
dc.identifier.isiWOS:000282304000048
Funding AgencyGrant Number
The University of Hong Kong
University Grants Council of HKSARAoE 10/01P
Hong Kong Research Grants CouncilHKU 1/CRF/08
HKU 7007/08P
Funding Information:

This work was supported by The University of Hong Kong (University Development Fund), the University Grants Council of HKSAR (the Area of Excellence Scheme: AoE 10/01P), and the Hong Kong Research Grants Council (HKU 1/CRF/08, HKU 7007/08P). We are grateful to Dr. Nianyong Zhu for assistance in solving the X-ray crystal structures of 1 center dot FeCl<INF>4</INF> and 1 center dot ClO<INF>4</INF>center dot MeCN.

 
dc.identifier.issn0002-7863
2013 Impact Factor: 11.444
 
dc.identifier.issue38
 
dc.identifier.openurl
 
dc.identifier.pmid20812697
 
dc.identifier.scopuseid_2-s2.0-77957121071
 
dc.identifier.spage13229
 
dc.identifier.urihttp://hdl.handle.net/10722/134389
 
dc.identifier.volume132
 
dc.languageeng
 
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.html
 
dc.publisher.placeUnited States
 
dc.relation.ispartofJournal of the American Chemical Society
 
dc.relation.referencesReferences in Scopus
 
dc.subject.meshAlkenes - chemistry
 
dc.subject.meshAza Compounds - chemistry
 
dc.subject.meshMacrocyclic Compounds - chemistry
 
dc.subject.meshSpectrometry, Mass, Electrospray Ionization - methods
 
dc.subject.meshSulfuric Acids - chemistry
 
dc.titleCis-dihydroxylation of alkenes with oxone catalyzed by iron complexes of a macrocyclic tetraaza ligand and reaction mechanism by ESI-MS spectrometry and DFT calculations
 
dc.typeArticle
 
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<description.abstract>[FeIII(L-N4Me2)Cl2]+ (1, L-N4Me2 = N,N&#8242;-dimethyl-2,11-diaza[3.3](2,6) pyridinophane) is an active catalyst for cis-dihydroxylation of various types of alkenes with oxone at room temperature using limiting amounts of alkene substrates. In the presence of 0.7 or 3.5 mol % of 1, reactions of electron-rich alkenes, including cyclooctene, styrenes, and linear alkenes, with oxone (2 equiv) for 5 min resulted in up to &gt;99% substrate conversion and afforded cis-diol products in up to 67% yield, with cis-diol/epoxide molar ratio of up to 16.8:1. For electron-deficient alkenes including &#945;,&#946;-unsaturated esters and &#945;,&#946;-unsaturated ketones, their reactions with oxone (2 equiv) catalyzed by 1 (3.5 mol %) for 5 min afforded cis-diols in up to 99% yield with up to &gt;99% substrate conversion. A large-scale cis-dihydroxylation of methyl cinnamate (9.7 g) with oxone (1 equiv) afforded the cis-diol product (8.4 g) in 84% yield with 85% substrate conversion. After catalysis, the L-N4Me2 ligand released due to demetalation can be reused to react with newly added Fe(ClO4)2&#8226;4H2O to generate an iron catalyst in situ, which could be used to restart the catalytic alkene cis-dihydroxylation. Mechanistic studies by ESI-MS, isotope labeling studies, and DFT calculations on the 1-catalyzed cis-dihydroxylation of dimethyl fumarate with oxone reveal possible involvement of cis-HO-Fe V O and/or cis-O FeV O species in the reaction; the cis-dihydroxylation reactions involving cis-HO-FeV O and cis-O FeV O species both proceed by a concerted but highly asynchronous mechanism, with that involving cis-HO-FeV O being more favorable due to a smaller activation barrier. &#169; 2010 American Chemical Society.</description.abstract>
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Author Affiliations
  1. Institute of Molecular Technology for Drug Discovery and Synthesis, Hong Kong